JP2008127294A - Pyrene-based compound, and organic photosensitive material, method for forming image and device for forming image each by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pyrene-based compound forming an electrostatic latent image formed by an image-exposing light source such as a semiconductor laser having 350 to 500 nm ocillation wavelength, highly minutely on an organic photosensitive material, reproducing the highly minutely formed electrostatic latent image as a toner image faithfully and forming a highly minute electronic photographic image suitable for a printing field, the organic photosensitive material, a method for forming the image and a device for forming image. <P>SOLUTION: This pyrene-based compound is provided by having ≤1.0% mass-decreasing rate at 400°C (D400) defined by the following formula in a thermal mass analysis. D400=ä(Gi-G400)/Gi}×100. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  An object of the present invention is to provide a pyrene compound having a novel physical property exhibiting high sensitivity as a charge generation material of an electrophotographic photoreceptor, and an organic photoreceptor, an image forming method and an image using the pyrene compound. More specifically, a pyrene compound having novel physical properties used in electrophotographic image formation used in the field of copying machines and printers, an organic photoreceptor using the pyrene compound, an image forming method, and the like The present invention relates to an image forming apparatus.

  In recent years, there are increasing opportunities to use electrophotographic copying machines and printers in the fields of printing and color printing. In the fields of printing and color printing, there is a strong tendency to demand high-quality digital monochrome images or color images. In response to such a demand, it has been proposed to form a high-definition digital image using a short wavelength laser beam as an exposure light source. However, even if the short-wavelength laser light is used to reduce the dot diameter of the exposure and a fine electrostatic latent image is formed on the electrophotographic photosensitive member, the finally obtained electrophotographic image has sufficient high image quality. The current situation has not been achieved.

  The cause is that the photosensitive characteristics of the electrophotographic photosensitive member and the charging characteristics of the toner of the developer do not have sufficient characteristics necessary for forming a fine dot latent image or forming a toner image.

  That is, as an electrophotographic photoreceptor, an organic photoreceptor developed for a conventional long wavelength laser (hereinafter, simply referred to as a photoreceptor) has poor sensitivity characteristics, and the exposure dot diameter is reduced using a short wavelength laser beam. When the narrowed image exposure is performed, the dot latent image is not clearly formed, and the reproducibility of the dot image tends to deteriorate.

  Conventionally, anthanthrone pigments and pyranthrone compounds are known as charge generation materials for photoreceptors for short wavelength lasers (Patent Document 1). However, the polycyclic quinone pigments such as the anthanthrone pigments described in the patent document simply have no special treatment, and are considered to be simply using commercially available pigments. The sensitivity and other characteristics that can be obtained using these commercially available pigments are sufficient for high-speed printers and copiers using short-wavelength lasers that are expected to be developed in the future. Not.

  It is also known to perform sublimation purification to increase the sensitivity of polycyclic quinone pigments (Patent Document 2). However, the sublimation purification method described in the patent document is a simple one-time sublimation purification method, and the pigment obtained by this sublimation purification is also a high-speed printer or copying machine using a short wavelength laser. However, sufficient sensitivity and high speed are not obtained.

Therefore, the inventors of the present application use a known pyrene compound (Patent Document 3) having a ring structure similar to a polycyclic quinone pigment and having a relatively high sensitivity on the short wavelength side as a charge generation material. Although a photoconductor for a short wavelength laser was prototyped, with a charge generating material of a pyrene compound obtained by the synthesis method described in the patent document, a high-speed printer or copying machine using a short wavelength laser Sufficient sensitivity and high speed are not obtained.
JP 2000-47408 A JP 57-67934 A Japanese Patent Laid-Open No. 5-301876

  The present invention has been made to solve the above problems. An object of the present invention is to form a high-density electrostatic latent image on an organic photoreceptor using image exposure of a semiconductor laser or a light emitting diode having an oscillation wavelength of 350 to 500 nm, and sensitivity, repeatability, or dot reproducibility. It is to provide a pyrene compound having novel physical properties used for an organic photoreceptor having improved deterioration of the organic material, and to provide an organic photoreceptor, an image forming method, and an image forming apparatus using the pyrene compound. is there.

  As a result of repeated studies on the above problems, the object of the present invention is to form a high-density electrostatic latent image on an organic photoreceptor using image exposure of a semiconductor laser or light emitting diode having an oscillation wavelength of 350 to 500 nm. In order to form an electrophotographic image with improved sensitivity, residual potential characteristics, dot reproducibility, etc., pyrene having novel physical properties with improved sensitivity characteristics against short-wavelength laser light, etc. The present invention has been completed by finding that it is effective to use an organic compound as a charge generating material for an organic photoreceptor. That is, for the above-mentioned problems that are likely to occur with exposure light of a short wavelength laser beam, it has been found that it is effective to use a pyrene compound exhibiting the thermal mass characteristics as described below, and the present invention has been completed. did.

That is, the present invention is achieved by using a pyrene compound or an organic photoreceptor having the following configuration.
(1) In thermal mass spectrometry, the mass decrease rate D400 at 400 ° C. defined by the following formula is 1.0% or less and contains at least one of the compounds of the following general formulas (1) to (3). A pyrene compound characterized by

D400 = {(Gi−G400) / Gi} × 100
However, Gi is the mass at the start of measurement, and G400 is the mass at 400 ° C.

(In the general formulas (1) to (3), X represents a substituted or unsubstituted divalent aromatic group or heterocyclic group, and R represents a substituted or unsubstituted monovalent aromatic group or heterocyclic group. To express.)
(2) The pyrene compound as described in 1 above, which is obtained by multi-stage sublimation purification.
(3) The pyrene compound as described in 1 above, which is obtained by fractional sublimation purification.
(4) The pyrene compound as described in 1 above, which is obtained by heat treatment in a high boiling point organic solvent.
(5) The pyrene compound as described in 1 above, which is obtained by an acid paste treatment.
(6) In an organic photoreceptor having a photosensitive layer on a conductive support, the photosensitive layer has a mass reduction rate D400 at 400 ° C. defined by the following formula of 1.0% or less, and the general formula (1) An organophotoreceptor comprising at least one pyrene compound of (3).

D400 = {(Gi−G400) / Gi} × 100
However, Gi is the mass at the start of measurement, and G400 is the mass at 400 ° C.

(In the general formulas (1) to (3), X represents a substituted or unsubstituted divalent aromatic group or heterocyclic group, and R represents a substituted or unsubstituted monovalent aromatic group or heterocyclic group. To express.)
(7) An exposure process for forming an electrostatic latent image on an organic photoreceptor using a semiconductor laser having an oscillation wavelength of 350 to 500 nm or a writing light source of a light emitting diode, and developing the electrostatic latent image into a toner image In the image forming method having a developing step, the organic photoreceptor has a photosensitive layer on a conductive support, and the mass reduction rate D400 at 400 ° C. defined by the following formula is 1.0. % Or less and containing at least one pyrene compound represented by the following general formulas (1) to (3).

D400 = {(Gi−G400) / Gi} × 100
However, Gi is the mass at the start of measurement, and G400 is the mass at 400 ° C.

(In the general formulas (1) to (3), X represents a substituted or unsubstituted divalent aromatic group or heterocyclic group, and R represents a substituted or unsubstituted monovalent aromatic group or heterocyclic group. To express.)
(8) An exposure unit for forming an electrostatic latent image on an organic photoconductor using a semiconductor laser having an oscillation wavelength of 350 to 500 nm or a light source of a light emitting diode, and developing the electrostatic latent image into a toner image In the image forming apparatus having the developing means, the organic photoreceptor has a photosensitive layer on a conductive support, and the mass reduction rate D400 at 400 ° C. defined by the following formula is 1% or less. And at least one pyrene compound represented by the following general formulas (1) to (3).

D400 = {(Gi−G400) / Gi} × 100
However, Gi is the mass at the start of measurement, and G400 is the mass at 400 ° C.

  (In the general formulas (1) to (3), X represents a substituted or unsubstituted divalent aromatic group or heterocyclic group, and R represents a substituted or unsubstituted monovalent aromatic group or heterocyclic group. To express.)

  In an electrophotographic image forming system using a short wavelength laser beam or the like by using an organic photoreceptor, an image forming method and an image forming apparatus containing the pyrene compound of the present invention, the potential attenuation value with respect to unit exposure amount is large and Repeatability is also good, a small-diameter dot latent image can be formed sharply, and an electrophotographic image with improved dot reproducibility can be formed.

  Hereinafter, the organic photoreceptor of the present invention will be described in detail.

  The pyrene compound of the present invention has a mass reduction rate D400 at 400 ° C. defined by the above formula of 1.0% or less and at least one of the compounds represented by the general formulas (1) to (3) in the thermal mass analysis. It is characterized by containing one.

  The present invention uses the pyrene compound having the thermal mass characteristics as described above as a charge generation material of an organic photoreceptor, thereby forming a high-definition dot image in an electrophotographic image forming system using a short wavelength laser beam or the like. Forming an electrophotographic image having a large potential attenuation value with respect to unit exposure, good repeatability, sharply forming a small-diameter dot latent image, and improved dot reproducibility. Can do.

  Hereinafter, the constituent requirements of the present invention will be described in detail.

  The pyrene compound of the present invention has a mass reduction rate D400 of 400 ° C. defined by the following formula in a thermal mass analysis of 1.0% or less.

D400 = {(Gi−G400) / Gi} × 100
However, Gi is the mass at the start of measurement, and G400 is the mass at 400 ° C.

  The mass reduction rate D400 is a mass reduction rate produced when the pyrene compound is heated from room temperature to 400 ° C. This measurement can be performed under the following conditions.

  About 5 mg of sample was heated at a rate of 10 ° C. per minute under a nitrogen stream of 100 ml / min by “differential thermogravimetric simultaneous measurement device TG / DTA6200” (manufactured by Seiko Instruments Inc.). The mass reduction rate that occurs when the temperature is raised to 400 ° C. from the start of measurement (room temperature) is measured.

  In the pyrene compounds of the general formulas (1) to (3), the mass reduction rate in the above temperature range seems to indicate the amount of impurity components that volatilize near the sublimation point of the pyrene compounds, If such an impurity component is contained in a large amount in a pigment of a pyrene compound, it is considered that a large amount of impurity levels are generated in the pigment, thereby deteriorating the sensitivity and repetitive characteristics of the photoreceptor.

  The organophotoreceptor according to the present invention contains a pyrene compound having a mass reduction rate of 1.0% by mass or less as a charge generation material. That is, the charge generating material of the pyrene compound contains at least one of the pyrene compounds of the general formulas (1) to (3).

  In the general formulas (1) to (3), X includes a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyridine ring, an anthraquinone ring, and the like, and particularly preferred are a benzene ring and a naphthalene ring. is there. Examples of the substituent on X include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acyl group, an acyloxy group, a halogen group, a nitro group, and a cyano group. Two Xs may be the same or different. Examples of R include substituted and unsubstituted phenyl groups, naphthalenyl groups, furyl groups, thienyl groups, and pyridyl groups. Particularly preferred are substituted and unsubstituted phenyl groups and naphthalenyl groups. Examples of the substituent on R include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acyl group, an acyloxy group, a halogen group, a nitro group, and a cyano group. Two Rs may be the same or different.

  These compounds have a large potential attenuation value per unit exposure amount with respect to an exposure light source having a wavelength of 350 to 500 nm, and can form a small dot latent image sharply.

  The pyrene compound represented by the general formula (1) to the general formula (3) includes a pyrene-1,2,6,7-tetracarboxylic dianhydride derivative represented by the following general formula (6) and a general formula. It is produced by a dehydration condensation reaction of the diamino compound represented by (7).

(In general formula (6), R is the same as in general formula (1) to general formula (3). In general formula (7), X is the same as in general formula (1) to general formula (3). .)
The pyrene compounds represented by the general formulas (1) to (3) are structural isomers of each other, and the compounds produced in the condensation reaction are produced as a mixture of these structural isomers. However, even if they are used without being isolated, the effects of the present invention can be exhibited well. In the specific examples of the general formulas (1) to (3) described below, it is assumed that each compound can take a structural isomer. In the examples described later, organic photoreceptors are produced using a mixture of structural isomers as they are.

  Specific examples of the pyrene compounds represented by the general formulas (1) to (3) are illustrated below.

  Next, synthesis examples of the above exemplary compounds will be described.

Synthesis Example 1 (CGM-1)
3,8-diphenylpyrene-1,2,6,7-tetracarboxylic dianhydride 2.5 g (0.005 mol), o-phenylenediamine 1.6 g (0.015 mol), anhydrous zinc chloride 1 g (0.001 mol) was heated to reflux in 50 ml of quinoline for 2 hours, and the precipitated crystals were collected by filtration. After washing with acetone and methanol, it was dried to obtain 2.8 g (88%) of exemplary compound CGM-1.

  Next, with respect to a method for purifying a pyrene compound having a mass reduction rate of 1.0% or less according to the present invention using the pyrene compound (pigment) obtained in Synthesis Example 1, the following a to d ( Specific description will be given in the purification treatments a to d) of the pyrene compound.

a. Pyrene compounds obtained by multi-stage sublimation purification Multi-stage sublimation purification includes two or more sublimation steps. The first stage condenses an effective amount, for example about 1-10% by weight of the sublimate, onto the first substrate at a temperature slightly above the sublimation temperature of the pigment. Subsequently, in the second stage, the sublimation temperature is raised in the range of 10 to 100 ° C., and the sublimate is condensed on the second substrate, whereby a high-purity pigment containing no volatile impurities or decomposition impurities can be obtained. Depending on the case, three or more steps may be included.

Purification Example 1 (Specific example of multi-stage sublimation purification)
After putting 5 g of the pyrene compound (CGM-1) obtained in Synthesis Example 1 into a crucible and depressurizing the chamber of the sublimation apparatus to about 10 ⁻³ to 10 ⁻⁴ Torr, the temperature of the crucible is raised at 420 ° C. Maintained for 10 minutes and stopped heating. When the temperature of the crucible became 200 ° C. or lower, the pressure in the chamber was changed to atmospheric pressure, and 0.5 g of sublimate (first stage sublimation CGM-1) was collected from the collector substrate. Next, after the pressure of the chamber of the sublimation apparatus was reduced to about 10 ⁻³ to 10 ⁻⁴ Torr, the temperature of the crucible was heated at 450 ° C. for 2 hours. After cooling, 4.2 g of a pyrene compound (second stage sublimation CGM-1) attached to the collector substrate was obtained. The mass reduction rate of the CGM-1 was 0.5%.

b. Pyrene-based compounds obtained by fractional sublimation purification In fractional sublimation purification, the pigment is first heated to a temperature T1 at a first position to evaporate the pigment and volatile impurities contained therein, and then maintained at a temperature T2 lower than T1. This is done by condensing the pigment vapor at the second position and then condensing the vapor of volatile impurities at the third position maintained at a temperature T3 lower than T2. Non-sublimable impurities remain in the first position with the starting material, and a purified pigment separated from volatile impurities is obtained. The fractional sublimation method of the present invention includes known purification methods such as train sublimation.

Purification example 2 (specific example of fractional sublimation purification)
5 g of the pyrene compound (CGM-1) obtained in Synthesis Example 1 was placed in a Pyrex (registered trademark) glass tube, and the tube was subjected to a temperature gradient (1 m) of about 480 ° C. to about 20 ° C. along the length of the tube. At a temperature gradient of about 480 ° C. to about 20 ° C.). The inside of the glass tube was depressurized to about 10 ⁻³ to 10 ⁻⁴ Torr, and the position where the pyrene pigment to be purified was placed was heated to about 480 ° C. The generated vapor was transferred to the low temperature side of the tube and condensed to obtain 4.4 g of a pyrene compound (CGM-1) sublimate condensed in a region between about 300 to 420 ° C. The mass reduction rate of the CGM-1 was 0.24%.

c. A pyrene compound obtained by heat treatment in a high-boiling solvent Heat treatment in a high-boiling solvent is a recrystallization or washing by heating an unpurified pigment in a high-boiling solvent having a boiling point of 150 ° C. or higher. It is to remove impurities that are highly soluble in the solvent. Preferred high boiling point solvents in the present invention include o-dichlorobenzene, 1-chloronaphthalene, nitrobenzene, quinoline, sulfolane and the like.

Purification Example 3 (Specific example of heat treatment in a high boiling point solvent)
After putting 5 g of the pyrene compound (CGM-1) obtained in Synthesis Example 1 into a crucible and depressurizing the chamber of the sublimation apparatus to about 10 ⁻³ to 10 ⁻⁴ Torr, the temperature of the crucible is raised to 450 ° C. and 2 Heated for hours. After cooling, the pressure inside the chamber was changed to atmospheric pressure to obtain 4.5 g of sublimate adhering to the collector substrate. Next, 1.0 g of the sublimate was suspended in 100 ml of quinoline, heated at 200 ° C. for 1 hour, filtered, washed with acetone and then methanol, and dried to obtain purified CGM-1. The mass reduction rate of the CGM-1 was 0.51%.

d. Pyrene-based compounds obtained by acid paste treatment Acid paste treatment is a process in which pigment is dissolved in a strong acid such as sulfuric acid, chlorosulfuric acid or trifluoroacetic acid and then poured into water to form fine particles, and at the same time, removal of water-soluble inorganic impurities and pigment particles This is a treatment that promotes the amorphization of the phthalocyanine, and is a treatment technique often used for phthalocyanine pigments. The acid paste treatment of the pyrene compound of the present invention is preferably performed using trifluoroacetic acid.

  Since the acid paste-treated pigment is a fine particle, the crystal after filtration after washing with water usually contains water 5 to 10 times the mass of the pigment and is obtained in the form of a wet cake or hydrous paste. Is dried to obtain the desired pigment.

Purification Example 4 (Specific example of acid paste treatment)
After putting 5 g of the pyrene compound (CGM-1) obtained in Synthesis Example 1 into a crucible and depressurizing the chamber of the sublimation apparatus to about 10 ⁻³ to 10 ⁻⁴ Torr, the temperature of the crucible is raised to 450 ° C. and 2 Heated for hours. After cooling, the pressure inside the chamber was changed to atmospheric pressure to obtain 4.5 g of sublimate adhering to the collector substrate. Next, 1.0 g of the sublimate was dissolved in 30 ml of trifluoroacetic acid, and this was added dropwise to 500 ml of water. The precipitated pigment was filtered, suspended in 200 ml of water and washed. Washing with water was repeated until the electric conductivity of the washing liquid reached 100 μS / cm or less, and the resulting wet cake was dried to obtain purified CGM-1. The mass reduction rate of the CGM-1 was 0.76%.

  The organophotoreceptor according to the present invention is an organophotoreceptor containing the charge generating material of the general formula (1). The constitution of the organophotoreceptor containing these charge generating materials will be described below.

  In the present invention, the organic photoconductor means an electrophotographic photoconductor constituted by providing an organic compound with at least one of a charge generation function and a charge transport function essential to the configuration of the electrophotographic photoconductor. All known organic photoconductors such as a photoconductor composed of an organic charge generating material or an organic charge transport material, a photoconductor composed of a polymer complex with a charge generating function and a charge transport function are contained.

The constitution of the organophotoreceptor of the present invention is not particularly limited as long as it contains the compound of the general formula (1) according to the present invention, and examples thereof include the following constitutions;
1) A structure in which a charge generation layer and a charge transport layer are sequentially laminated as a photosensitive layer on a conductive support;
2) A structure in which a charge generation layer, a first charge transport layer, and a second charge transport layer are sequentially laminated as a photosensitive layer on a conductive support;
3) A structure in which a single layer containing a charge transport material and a charge generation material is formed as a photosensitive layer on a conductive support;
4) A structure in which a charge transport layer and a charge generation layer are sequentially laminated as a photosensitive layer on a conductive support;
5) A structure in which a surface protective layer is further formed on the photosensitive layer of the photoreceptors 1) to 5) above.

  The photoconductor may have any of the above configurations. The surface layer of the photoreceptor is a layer in contact with the air interface. When only a single-layer photosensitive layer is formed on the conductive support, the photosensitive layer is the surface layer, and the conductive layer In the case where a single-layered or laminated photosensitive layer and a surface protective layer are laminated on the conductive support, the surface protective layer is the outermost surface layer. In the present invention, the configuration 2) is most preferably used. Note that, regardless of the configuration of the photoreceptor of the present invention, an undercoat layer (intermediate layer) may be formed on the conductive support prior to the formation of the photosensitive layer.

  The charge transport layer means a layer having a function of transporting charge carriers generated in the charge generation layer by photoexposure to the surface of the organic photoreceptor, and the specific detection of the charge transport function is carried out between the charge generation layer and the charge transport layer. It can be confirmed by laminating a transport layer on a conductive support and detecting optical conductivity.

  Next, the layer structure of the organic photoreceptor will be described focusing on the structure of 1) above.

Conductive Support The conductive support used for the photoreceptor may be either a sheet or a cylinder, but a cylindrical conductive support is preferred for designing an image forming apparatus compactly. .

  Cylindrical conductive support means a cylindrical support necessary for forming an endless image by rotating. Conductivity is within a range of 0.1 mm or less in straightness and 0.1 mm or less in deflection. A support is preferred. Exceeding the range of straightness and shake makes it difficult to form a good image.

  As the conductive material, a metal drum such as aluminum or nickel, a plastic drum deposited with aluminum, tin oxide, indium oxide or the like, or a paper / plastic drum coated with a conductive substance can be used. The conductive support preferably has a specific resistance of 103 Ωcm or less at room temperature. The conductive support of the present invention is most preferably an aluminum support. As the aluminum support, one in which components such as manganese, zinc, magnesium and the like are mixed in addition to the main component aluminum is also used.

Intermediate layer In the present invention, an intermediate layer is preferably provided between the conductive support and the photosensitive layer.

  The intermediate layer used in the present invention preferably contains N-type semiconductor particles. The N-type semiconductive particle means a particle whose main charge carrier is an electron. That is, since the main charge carriers are electrons, the intermediate layer containing the N-type semiconductive particles in the insulating binder effectively blocks hole injection from the substrate, and the electrons from the photosensitive layer. In contrast, it has a property of low blocking.

  As the N-type semiconductor particles, titanium oxide (TiO2) and zinc oxide (ZnO) are preferable, and titanium oxide is particularly preferably used.

  As the N-type semiconductor particles, fine particles having a number average primary particle size in the range of 3.0 to 200 nm are used. Particularly, 5 nm to 100 nm is preferable. The number average primary particle diameter is a measured value as an average diameter in the ferret direction by observing 100 particles as primary particles at random by magnifying the fine particles 10,000 times by transmission electron microscope observation and image analysis. N-type semiconducting particles having a number average primary particle size of less than 3.0 nm are difficult to uniformly disperse in the intermediate layer binder, and easily form aggregated particles. Is likely to occur. On the other hand, N-type semiconducting particles having a number average primary particle size larger than 200 nm tend to make large irregularities on the surface of the intermediate layer, and the dot image tends to deteriorate through these large irregularities. In addition, the N-type semiconductive particles having a number average primary particle size larger than 200 nm are likely to precipitate in the dispersion and easily generate aggregates. As a result, the dot image tends to deteriorate.

  The titanium oxide particles have anatase, rutile, brookite, and amorphous forms as crystal forms. Among them, the rutile form titanium oxide pigment or the anatase form titanium oxide pigment has a rectifying property of charge passing through the intermediate layer. In other words, the mobility of electrons is increased, the charging potential is stabilized, the residual potential is prevented from increasing, and the dot image is prevented from deteriorating, which is most preferable as the N-type semiconductor particles of the present invention. .

  N-type semiconductive particles are preferably surface-treated with a polymer containing methylhydrogensiloxane units. The molecular weight of the polymer containing the methyl hydrogen siloxane unit is 1000 to 20000, and the surface treatment effect is high. As a result, the rectifying property of the N-type semiconductor particles is improved, and the N-type semiconductor particles are contained. By using the intermediate layer, the occurrence of black spots is prevented and there is an effect on the reproducibility of good dot images.

The polymer containing a methylhydrogensiloxane unit is preferably a copolymer of a structural unit of-(HSi (CH ₃ ) O)-and a structural unit other than this (other siloxane unit). As other siloxane units, dimethylsiloxane units, methylethylsiloxane units, methylphenylsiloxane units, diethylsiloxane units, and the like are preferable, and dimethylsiloxane is particularly preferable. The proportion of methylhydrogensiloxane units in the copolymer is 10 to 99 mol%, preferably 20 to 90 mol%.

  The methylhydrogensiloxane copolymer may be any of a random copolymer, a block copolymer, a graft copolymer, etc., but a random copolymer and a block copolymer are preferred. In addition to methylhydrogensiloxane, the copolymerization component may be one component or two or more components.

  The intermediate layer coating solution prepared for forming the intermediate layer used in the present invention is composed of a binder resin, a dispersion solvent and the like in addition to the N-type semiconductive particles such as the surface-treated titanium oxide.

  The ratio of the N-type semiconductive particles in the intermediate layer is preferably 1.0 to 2.0 times in terms of the volume ratio of the intermediate layer to the binder resin (when the volume of the binder resin is 1). By using the N-type semiconductor particles of the present invention at such a high density in the intermediate layer, the rectification property of the intermediate layer is increased, and the increase in residual potential and dot image deterioration are effective even when the film thickness is increased. Therefore, a good organic photoreceptor can be formed. Further, such an intermediate layer preferably uses 100 to 200 parts by volume of N-type semiconductive particles with respect to 100 parts by volume of the binder resin.

  On the other hand, the binder resin in which these particles are dispersed to form the layer structure of the intermediate layer is preferably a polyamide resin in order to obtain good dispersibility of the particles, but the polyamide resin shown below is particularly preferable.

  The binder resin for the intermediate layer is preferably an alcohol-soluble polyamide resin. As the binder resin for the intermediate layer of the organic photoreceptor, a resin having excellent solvent solubility is required in order to form the intermediate layer with a uniform film thickness. As such alcohol-soluble polyamide resins, copolymerized polyamide resins and methoxymethylated polyamide resins composed of a chemical structure with few carbon chains between amide bonds such as 6-nylon described above are known. Surprisingly, the following polyamides can also be preferably used.

  The molecular weight of the polyamide resin is preferably 5,000 to 80,000, more preferably 10,000 to 60,000 in terms of number average molecular weight. When the number average molecular weight is 5,000 or less, the uniformity of the film thickness of the intermediate layer is deteriorated, and the effects of the present invention are not sufficiently exhibited. On the other hand, if it is larger than 80,000, the solvent solubility of the resin is likely to be reduced, and an agglomerated resin is likely to be generated in the intermediate layer.

  A part of the polyamide resin is already available on the market. For example, the polyamide resin is sold under the trade names such as Vestamelt X1010 and X4685 manufactured by Daicel Degussa Co., Ltd., and can be produced by a general synthesis method of polyamide. However, an example of a synthesis example is given below.

  As the solvent for dissolving the polyamide resin and preparing the coating solution, alcohols having 2 to 4 carbon atoms such as ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, t-butanol, sec-butanol are preferable, It is excellent in the solubility of polyamide and the coating property of the prepared coating solution. These solvents are 30 to 100% by mass, preferably 40 to 100% by mass, and more preferably 50 to 100% by mass in the total solvent. Examples of co-solvents that can be used in combination with the above-mentioned solvent to obtain preferable effects include methanol, benzyl alcohol, toluene, methylene chloride, cyclohexanone, and tetrahydrofuran.

  The thickness of the intermediate layer of the present invention is preferably 0.3 to 10 μm. If the thickness of the intermediate layer is less than 0.5 μm, black spot is likely to occur and the dot image is likely to deteriorate. If it exceeds 10 μm, the residual potential is likely to increase, and the dot image tends to deteriorate. As for the film thickness of an intermediate | middle layer, 0.5-5 micrometers is more preferable.

Moreover, it is preferable that the said intermediate | middle layer is an insulating layer substantially. Here, the insulating layer has a volume resistance of 1 × 10 8 or more. The volume resistance of the intermediate layer and the protective layer of the present invention is preferably 1 × 10 ⁸ to 10 ¹⁵ Ω · cm, more preferably 1 × 10 ⁹ to 10 ¹⁴ Ω · cm, and further preferably 2 × 10 ⁹ to 1 ×. 10 ¹³ Ω · cm. The volume resistance can be measured as follows.

  Measurement conditions: According to JIS: C2318-1975.

Measuring instrument: Hiresta IP manufactured by Mitsubishi Yuka
Measurement conditions: Measurement probe HRS
Applied voltage: 500V
Measurement environment: 30 ± 2 ℃, 80 ± 5RH%
If the volume resistance is less than 1 × 10 8, the charge blocking property of the intermediate layer decreases, the occurrence of black spots increases, the potential holding property of the organic photoreceptor deteriorates, and good image quality cannot be obtained. On the other hand, if it is larger than 1015 Ω · cm, the residual potential tends to increase in repeated image formation, and good image quality cannot be obtained.

Photosensitive layer The photosensitive layer configuration of the photoreceptor of the present invention may be a single-layer photosensitive layer configuration in which a charge generation function and a charge transport function are provided on one layer on the intermediate layer, but more preferably the function of the photosensitive layer. The charge generation layer (CGL) and the charge transport layer (CTL) may be separated from each other. By adopting a configuration in which the functions are separated, an increase in the residual potential due to repeated use can be controlled to be small, and other electrophotographic characteristics can be easily controlled according to the purpose. In the negatively charged photoconductor, it is preferable that a charge generation layer (CGL) is formed on the intermediate layer and a charge transport layer (CTL) is formed thereon.

  The structure of the photosensitive layer of the function-separated negatively charged photoreceptor will be described below.

Charge generation layer In the organic photoreceptor of the present invention, the charge generation material described above having high sensitivity characteristics in the wavelength region of 350 nm to 500 nm is used as the charge generation material. In addition to this charge generation material, other charge generation materials may be used in combination as required. Examples of the pigment used in combination include azo pigments, perylene pigments, and multisensitive quinone pigments.

  When a binder is used as the CGM dispersion medium in the charge generation layer, a known resin can be used as the binder, but the most preferred resins include formal resin, butyral resin, silicone resin, silicone-modified butyral resin, phenoxy resin, and the like. Can be mentioned. The ratio of the binder resin to the charge generating material is preferably 20 to 600 parts by mass with respect to 100 parts by mass of the binder resin. By using these resins, the increase in residual potential associated with repeated use can be minimized. The thickness of the charge generation layer is preferably 0.3 μm to 2 μm.

Charge Transport Layer In the present invention, the charge transport layer may be composed of a plurality of charge transport layers, and the uppermost charge transport layer may contain the inorganic fine particles of the present invention.

  The charge transport layer contains a charge transport material (CTM) and a binder resin that disperses and forms a CTM. As other substances, additives such as an antioxidant may be contained in addition to the inorganic fine particles as necessary.

  As the charge transport material (CTM), a known hole transport property (P-type) charge transport material (CTM) is preferably used. For example, a triphenylamine derivative, a hydrazone compound, a styryl compound, a benzidine compound, a butadiene compound, or the like can be used. These charge transport materials are usually dissolved in a suitable binder resin to form a layer. In particular, a charge transport material that does not absorb the wavelength of laser light for image exposure is preferably used. Examples of the charge transport material preferably used in the present invention include the following compounds.

  As the charge transport material (CTM), a known hole transport property (P-type) charge transport material (CTM) can be used. For example, a triphenylamine derivative, a hydrazone compound, a styryl compound, a benzidine compound, a butadiene compound, or the like can be used. These charge transport materials are usually dissolved in a suitable binder resin to form a layer.

  The binder resin used for the charge transport layer (CTL) may be either a thermoplastic resin or a thermosetting resin. For example, polystyrene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, polyvinyl butyral resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, polycarbonate resin, silicone resin, melamine resin, and these resins A copolymer resin containing two or more of the repeating unit structures. In addition to these insulating resins, high molecular organic semiconductors such as poly-N-vinylcarbazole can be used. Of these, polycarbonate resins are most preferred because of their low water absorption and good CTM dispersibility and electrophotographic characteristics.

  The ratio of the binder resin to the charge transport material is preferably 50 to 200 parts by mass with respect to 100 parts by mass of the binder resin.

  The total film thickness of the charge transport layer is preferably 10 to 30 μm. If the total film thickness is less than 10 μm, it is difficult to sufficiently obtain the latent image potential during development, and the image density and the dot reproducibility are liable to be deteriorated. Diffusion of charge carriers generated in the generation layer) increases, and dot reproducibility tends to deteriorate. Further, when the charge transport layer is formed of a plurality of layers, the thickness of the charge transport layer serving as the surface layer is preferably 1.0 to 8.0 μm.

  Solvents or dispersion media used to form layers such as intermediate layers, charge generation layers, and charge transport layers include n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N-dimethylformamide, acetone , Methyl ethyl ketone, methyl isopropyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, dichloromethane, 1,2-dichloroethane, 1,2-dichloropropane, 1,1,2-trichloroethane, 1,1,1-trichloroethane, trichloroethylene, Tetrachloroethane, tetrahydrofuran, dioxolane, dioxane, methanol, ethanol, butanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, methyl cello Lube, and the like. Although this invention is not limited to these, Solvents friendly to global environment, such as tetrahydrofuran and methyl ethyl ketone, are used preferably. These solvents may be used alone or as a mixed solvent of two or more.

  Next, as a coating processing method for producing the organic photoreceptor, a coating processing method such as dip coating or spray coating is used in addition to the slide hopper type coating device.

  Among the above coating liquid supply type coating apparatuses, the coating method using a slide hopper type coating apparatus is most suitable when the above-described dispersion using a low boiling point solvent is used as the coating liquid, and is a cylindrical photoconductor. In this case, the coating is preferably performed using a circular slide hopper type coating apparatus described in detail in JP-A No. 58-189061 and the like.

  The surface layer of the photoreceptor according to the present invention preferably contains an antioxidant. The surface layer is easily oxidized by an active gas such as NOx or ozone during charging of the photoconductor, and image blur is likely to occur. However, the presence of an antioxidant can prevent image blur. Typical examples of the antioxidants are those that prevent the action of oxygen under conditions of light, heat, discharge, etc. on auto-oxidizing substances present in the organic photoreceptor or on the surface of the organic photoreceptor, It is a substance that has the property of inhibiting.

  Solvents or dispersion media used to form layers such as intermediate layers, charge generation layers, and charge transport layers include n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N-dimethylformamide, acetone , Methyl ethyl ketone, methyl isopropyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, dichloromethane, 1,2-dichloroethane, 1,2-dichloropropane, 1,1,2-trichloroethane, 1,1,1-trichloroethane, trichloroethylene, Tetrachloroethane, tetrahydrofuran, dioxolane, dioxane, methanol, ethanol, butanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, methyl cello Lube, and the like. Although this invention is not limited to these, Dichloromethane, 1, 2- dichloroethane, methyl ethyl ketone, etc. are used preferably. These solvents may be used alone or as a mixed solvent of two or more.

  Next, an image forming apparatus using the organic photoreceptor according to the present invention will be described.

  An image forming apparatus 1 shown in FIG. 1 is a digital image forming apparatus, and includes an image reading unit A, an image processing unit B, an image forming unit C, and a transfer paper transport unit D as a transfer paper transport unit. Yes.

  The upper part of the image reading unit A is provided with automatic document feeding means for automatically conveying the document. The document placed on the document placing table 11 is separated and conveyed by the document conveying roller 12 to the reading position 13a. The image is read. The document after the document reading is completed is discharged onto the document discharge tray 14 by the document transport roller 12.

  On the other hand, the image of the original when placed on the platen glass 13 is read at a speed v of the first mirror unit 15 including the illumination lamp and the first mirror constituting the scanning optical system, and the V-shaped first image is located. Reading is performed by the movement of the second mirror unit 16 including the two mirrors and the third mirror in the same direction at the speed v / 2.

  The read image is formed on the light receiving surface of the image sensor CCD, which is a line sensor, through the projection lens 17. The line-shaped optical image formed on the image sensor CCD is sequentially photoelectrically converted into an electric signal (luminance signal) and then A / D converted, and the image processing unit B performs processing such as density conversion and filter processing. Then, the image data is temporarily stored in the memory.

  In the image forming unit C, as an image forming unit, a drum-shaped photoconductor 21 as an image carrier, a charging means (charging step) 22 for charging the photoconductor 21 on the outer periphery thereof, and a surface potential of the charged photoconductor. Potential detecting means 220 for detecting the toner, developing means (developing process) 23, transfer conveying belt device 45 as a transferring means (transfer process), cleaning device (cleaning process) 26 for the photosensitive member 21, and light neutralizing means (light slow charge). PCL (precharge lamp) 27 as a process is arranged in the order of operation. Further, on the downstream side of the developing means 23, a reflection density detecting means 222 for measuring the reflection density of the patch image developed on the photosensitive member 21 is provided. As the photosensitive member 21, the organic photosensitive member according to the present invention is used, and the photosensitive member 21 is driven and rotated in the clockwise direction shown in the drawing.

  After the rotating photosensitive member 21 is uniformly charged by the charging unit 22, an image based on an image signal called from the memory of the image processing unit B by an exposure optical system as an image exposure unit (image exposure step) 30 is used. Exposure is performed. The exposure optical system as the image exposure means 30 as the writing means uses a laser diode (not shown) as a light source, and the optical path is bent by the reflection mirror 32 via the rotating polygon mirror 31, the fθ lens 34, and the cylindrical lens 35, and main scanning is performed. Therefore, image exposure is performed on the photoconductor 21 at the position Ao, and an electrostatic latent image is formed by rotation (sub-scanning) of the photoconductor 21. In one example of the present embodiment, the character portion is exposed to form an electrostatic latent image.

  In the image forming apparatus of the present invention, a semiconductor laser or a light emitting diode having an oscillation wavelength of 350 to 500 nm is used as an image exposure light source when an electrostatic latent image is formed on a photoreceptor. Using these image exposure light sources, the exposure dot diameter in the writing direction is narrowed down to 10 to 50 μm, and digital exposure is performed on the organic photoreceptor, so that it is 600 dpi (dpi: the number of dots per 2.54 cm) or more. A high-resolution electrophotographic image of 2500 dpi can be obtained.

  The exposure dot diameter refers to the length of the exposure beam along the main scanning direction (Ld: measured at the maximum length) in a region where the intensity of the exposure beam is 1 / e 2 or more of the peak intensity.

  The light beam used includes a scanning optical system using a semiconductor laser and an LED solid state scanner. The light intensity distribution includes a Gaussian distribution and a Lorentz distribution. The exposure dot diameter according to the invention is used.

  The electrostatic latent image on the photoconductor 21 is reversely developed by the developing unit 23, and a visible toner image is formed on the surface of the photoconductor 21. In the image forming method of the present invention, it is preferable to use a polymerized toner as a developer used in the developing means. By using a polymer toner having a uniform shape and particle size distribution in combination with the organic photoreceptor according to the present invention, an electrophotographic image with better sharpness can be obtained.

  The electrostatic latent image formed on the organic photoreceptor of the present invention is visualized as a toner image by development. The toner used for development may be a pulverized toner or a polymerized toner, but the toner according to the present invention is preferably a polymerized toner that can be prepared by a polymerization method from the viewpoint of obtaining a stable particle size distribution.

  The term “polymerized toner” means a toner in which a toner binder resin is formed and the toner shape is formed by polymerization of a raw material monomer of the binder resin and, if necessary, subsequent chemical treatment. More specifically, it means a toner formed through a polymerization reaction such as suspension polymerization or emulsion polymerization, and if necessary, a step of fusing particles between them.

  The volume average particle diameter of the toner, that is, the 50% volume particle diameter (Dv50) is preferably 2 to 9 μm, more preferably 3 to 7 μm. By setting this range, the resolution can be increased. In addition, by combining with the above range, the amount of toner having a fine particle diameter can be reduced while being a small particle diameter toner, the dot image reproducibility is improved over a long period of time, and the sharpness is excellent. In addition, a stable image can be formed.

  The toner according to the present invention may be used as a one-component developer or a two-component developer.

  When used as a one-component developer, a non-magnetic one-component developer or a magnetic one-component developer containing about 0.1 to 0.5 μm of magnetic particles in the toner can be used. be able to.

  Further, it can be mixed with a carrier and used as a two-component developer. In this case, conventionally known materials such as metals such as iron, ferrite and magnetite, and alloys of these metals with metals such as aluminum and lead can be used as the magnetic particles of the carrier. Ferrite particles are particularly preferable. The magnetic particles preferably have a volume average particle size of 15 to 100 μm, more preferably 25 to 80 μm.

  The volume average particle diameter of the carrier can be typically measured by a laser diffraction particle size distribution measuring apparatus “HELOS” (manufactured by SYMPATEC) equipped with a wet disperser.

  The carrier is preferably a carrier in which magnetic particles are further coated with a resin, or a so-called resin dispersion type carrier in which magnetic particles are dispersed in a resin. The resin composition for coating is not particularly limited, and for example, olefin resin, styrene resin, styrene-acrylic resin, silicone resin, ester resin, or fluorine-containing polymer resin is used. In addition, the resin for constituting the resin-dispersed carrier is not particularly limited, and a known resin can be used. For example, a styrene-acrylic resin, a polyester resin, a fluorine resin, a phenol resin, or the like is used. be able to.

  In the transfer paper transport section D, paper feed units 41 (A), 41 (B), and 41 (C) are provided below the image forming unit as transfer paper storage means for storing transfer paper P of different sizes. Further, a manual paper feeding unit 42 for manually feeding paper is provided on the side, and the transfer paper P selected from any of them is fed along the transport path 40 by the guide roller 43 and fed. The transfer paper P is temporarily stopped by a pair of paper feed registration rollers 44 that correct the inclination and bias of the transfer paper P to be transferred, and then fed again. The transport path 40, the pre-transfer roller 43a, and the paper feed path 46 The toner image on the photosensitive member 21 is transferred to the transfer paper P while being transferred to the transfer conveyance belt 454 of the transfer conveyance belt device 45 by the transfer electrode 24 and the separation electrode 25 at the transfer position Bo. Is, transfer sheet P is separated from the photosensitive member 21 surface, it is conveyed to the fixing unit 50 by the transfer conveyor belt device 45.

  The fixing unit 50 includes a fixing roller 51 and a pressure roller 52. By passing the transfer paper P between the fixing roller 51 and the pressure roller 52, the toner is fixed by heating and pressing. After the toner image has been fixed, the transfer paper P is discharged onto the paper discharge tray 64.

  The above describes the state in which image formation is performed on one side of the transfer paper. However, in the case of double-sided copying, the paper discharge switching member 170 is switched, the transfer paper guide 177 is opened, and the transfer paper P is indicated by a broken arrow. Conveyed in the direction.

  Further, the transfer paper P is transported downward by the transport mechanism 178 and switched back by the transfer paper reversing unit 179, and the rear end portion of the transfer paper P becomes the leading end portion and transported into the duplex copying paper supply unit 130. The

  The transfer paper P is moved in a paper feed direction by a conveyance guide 131 provided in the double-sided copy paper supply unit 130, the transfer paper P is re-fed by the paper supply roller 132, and the transfer paper P is guided to the conveyance path 40. .

  Again, as described above, the transfer paper P is conveyed in the direction of the photosensitive member 21, the toner image is transferred to the back surface of the transfer paper P, fixed by the fixing unit 50, and then discharged onto the paper discharge tray 64.

  The image forming apparatus of the present invention is configured by integrally combining the above-described photosensitive member and components such as a developing device and a cleaning device as a process cartridge, and this unit is configured to be detachable from the apparatus main body. Also good. In addition, a process cartridge is formed by integrally supporting at least one of a charger, an image exposure device, a developing device, a transfer or separation device, and a cleaning device together with a photosensitive member, and a single unit that is detachable from the apparatus main body. It is good also as a structure which can be attached or detached using guide means, such as a rail of an apparatus body.

  FIG. 2 is a cross-sectional configuration diagram of a color image forming apparatus showing an embodiment of the present invention.

  This color image forming apparatus is called a tandem type color image forming apparatus, and includes four sets of image forming units (image forming units) 10Y, 10M, 10C, and 10Bk, an endless belt-shaped intermediate transfer body unit 7, and a feeding unit. It comprises a paper conveying means 21 and a fixing means 24. A document image reading device SC is disposed on the upper part of the main body A of the image forming apparatus.

  The image forming unit 10Y that forms a yellow image includes a charging unit (charging step) 2Y, an exposure unit (exposure step) 3Y, and a developing unit disposed around a drum-shaped photoconductor 1Y as a first image carrier. A unit (developing step) 4Y, a primary transfer roller 5Y as a primary transfer unit (primary transfer step), and a cleaning unit 6Y. An image forming unit 10M that forms a magenta image includes a drum-shaped photosensitive member 1M as a first image carrier, a charging unit 2M, an exposure unit 3M, a developing unit 4M, a primary transfer roller 5M as a primary transfer unit, It has a cleaning means 6M. An image forming unit 10C for forming a cyan image includes a drum-shaped photoreceptor 1C as a first image carrier, a charging unit 2C, an exposure unit 3C, a developing unit 4C, and a primary transfer roller 5C as a primary transfer unit. It has cleaning means 6C. The image forming unit 10Bk that forms a black image includes a drum-shaped photoreceptor 1Bk as a first image carrier, a charging unit 2Bk, an exposure unit 3Bk, a developing unit 4Bk, a primary transfer roller 5Bk as a primary transfer unit, and a cleaning unit. 6Bk.

  The four sets of image forming units 10Y, 10M, 10C, and 10Bk include charging means 2Y, 2M, 2C, and 2Bk that rotate around the photosensitive drums 1Y, 1M, 1C, and 1Bk, and image exposure means 3Y, 3M, 3C and 3Bk, rotating developing means 4Y, 4M, 4C and 4Bk, and cleaning means 5Y, 5M, 5C and 5Bk for cleaning the photosensitive drums 1Y, 1M, 1C and 1Bk.

  The image forming units 10Y, 10M, 10C, and 10Bk have the same configuration except that the colors of toner images formed on the photoreceptors 1Y, 1M, 1C, and 1Bk are different, and the image forming unit 10Y is taken as an example in detail. explain.

  The image forming unit 10Y has a charging unit 2Y (hereinafter simply referred to as a charging unit 2Y or a charger 2Y), an exposure unit 3Y, a developing unit 4Y, and a cleaning unit 5Y (around a photosensitive drum 1Y as an image forming body). Hereinafter, the cleaning means 5Y or the cleaning blade 5Y) is simply disposed, and a yellow (Y) toner image is formed on the photosensitive drum 1Y. In the present embodiment, in the image forming unit 10Y, at least the photosensitive drum 1Y, the charging unit 2Y, the developing unit 4Y, and the cleaning unit 5Y are provided so as to be integrated.

  The charging unit 2Y is a unit that applies a uniform potential to the photosensitive drum 1Y. In the present embodiment, a corona discharge type charger 2Y is used for the photosensitive drum 1Y.

  The image exposure means 3Y performs exposure based on the image signal (yellow) on the photosensitive drum 1Y given a uniform potential by the charger 2Y, and forms an electrostatic latent image corresponding to the yellow image. As the exposure means 3Y, the exposure means 3Y includes an LED in which light emitting elements are arranged in an array in the axial direction of the photosensitive drum 1Y and an imaging element (trade name; Selfoc lens), or A laser optical system or the like is used.

  The image forming apparatus of the present invention is constructed by integrally combining the above-described photosensitive member and components such as a developing device and a cleaning device as a process cartridge (image forming unit). It may be configured to be detachable. In addition, at least one of a charging device, an image exposure device, a developing device, a transfer or separation device, and a cleaning device is integrally supported together with a photosensitive member to form a process cartridge (image forming unit), which is detachable from the apparatus main body. A single image forming unit may be detachable using guide means such as a rail of the apparatus main body.

  The endless belt-like intermediate transfer body unit 7 includes an endless belt-like intermediate transfer body 70 as a second image carrier having a semiconductive endless belt shape that is wound around a plurality of rollers and is rotatably supported.

  Each color image formed by the image forming units 10Y, 10M, 10C, and 10Bk is sequentially transferred onto a rotating endless belt-shaped intermediate transfer body 70 by primary transfer rollers 5Y, 5M, 5C, and 5Bk as primary transfer means. Thus, a synthesized color image is formed. A transfer material P as a transfer material (a support for carrying a fixed final image: for example, plain paper, a transparent sheet, etc.) housed in the paper feed cassette 20 is fed by a paper feed means 21 and a plurality of intermediates. After passing through rollers 22A, 22B, 22C, 22D and registration roller 23, they are conveyed to a secondary transfer roller 5b as a secondary transfer means, and are secondarily transferred onto a transfer material P to transfer a color image all at once. The transfer material P onto which the color image has been transferred is subjected to fixing processing by the fixing unit 24, is sandwiched between paper discharge rollers 25, and is placed on a paper discharge tray 26 outside the apparatus. Here, a transfer support for a toner image formed on a photosensitive member such as an intermediate transfer member or a transfer material is collectively referred to as a transfer medium.

  On the other hand, after the color image is transferred to the transfer material P by the secondary transfer roller 5b as the secondary transfer means, the residual toner is removed by the cleaning means 6b from the endless belt-shaped intermediate transfer body 70 in which the transfer material P is separated by curvature. The

  During the image forming process, the primary transfer roller 5Bk is always in contact with the photoreceptor 1Bk. The other primary transfer rollers 5Y, 5M, and 5C are in contact with the corresponding photoreceptors 1Y, 1M, and 1C, respectively, only during color image formation.

  The secondary transfer roller 5b contacts the endless belt-shaped intermediate transfer body 70 only when the transfer material P passes through the secondary transfer roller 5b.

  Further, the housing 8 can be pulled out from the apparatus main body A through the support rails 82L and 82R.

  The housing 8 includes image forming units 10Y, 10M, 10C, and 10Bk and an endless belt-shaped intermediate transfer body unit 7.

  The image forming units 10Y, 10M, 10C, and 10Bk are arranged in tandem in the vertical direction. An endless belt-shaped intermediate transfer body unit 7 is disposed on the left side of the photoreceptors 1Y, 1M, 1C, and 1Bk in the drawing. The endless belt-shaped intermediate transfer body unit 7 includes an endless belt-shaped intermediate transfer body 70 that can be rotated by winding rollers 71, 72, 73, 74, primary transfer rollers 5Y, 5M, 5C, 5Bk, and cleaning means 6b. Consists of.

  Next, FIG. 3 shows a color image forming apparatus using the organic photoreceptor of the present invention (a copying machine having at least a charging means, an exposure means, a plurality of developing means, a transfer means, a cleaning means, and an intermediate transfer body around the organic photoreceptor. 1 is a cross-sectional view of a configuration of a laser beam printer). The belt-shaped intermediate transfer body 70 uses an elastic body having a medium resistance.

  Reference numeral 1 denotes a rotary drum type photoconductor that is repeatedly used as an image forming body, and is rotationally driven in a counterclockwise direction indicated by an arrow at a predetermined peripheral speed.

  In the rotation process, the photoreceptor 1 is uniformly charged to a predetermined polarity and potential by a charging means (charging process) 2, and then time-series electric digital of image information by an image exposure means (image exposure process) 3 (not shown). An electrostatic latent image corresponding to the yellow (Y) color component image (color information) of the target color image is formed by receiving image exposure by scanning exposure light or the like by a laser beam modulated in accordance with the pixel signal. The

  Next, the electrostatic latent image is developed with yellow toner as the first color by yellow (Y) developing means: developing step (yellow color developing device) 4Y. At this time, the second to fourth developing means (magenta developer, cyan developer, black developer) 4M, 4C, and 4Bk are not activated and do not act on the photoreceptor 1. The yellow toner image of the first color is not affected by the second to fourth developing devices.

  The intermediate transfer member 70 is stretched by rollers 79a, 79b, 79c, 79d, and 79e, and is driven to rotate in the clockwise direction at the same peripheral speed as the photosensitive member 1.

  The yellow toner image of the first color formed and supported on the photosensitive member 1 is applied to the intermediate transfer member 70 from the primary transfer roller 5a in the process of passing through the nip portion between the photosensitive member 1 and the intermediate transfer member 70. The intermediate transfer (primary transfer) is sequentially performed on the outer peripheral surface of the intermediate transfer body 70 by the electric field formed by the primary transfer bias.

  The surface of the photoreceptor 1 after the transfer of the first color yellow toner image corresponding to the intermediate transfer body 70 is cleaned by the cleaning device 6a.

  Similarly, the second color magenta toner image, the third color cyan toner image, and the fourth color black (black) toner image are sequentially superimposed and transferred onto the intermediate transfer body 70 to correspond to the target color image. A superimposed color toner image is formed.

  The secondary transfer roller 5b is supported in parallel with the secondary transfer counter roller 79b so as to be separated from the lower surface portion of the intermediate transfer body 70.

  The primary transfer bias for sequentially superimposing and transferring the first to fourth color toner images from the photosensitive member 1 to the intermediate transfer member 70 has a polarity opposite to that of the toner and is applied from a bias power source. The applied voltage is, for example, in the range of +100 V to +2 kV.

  In the primary transfer process of the first to third color toner images from the photosensitive member 1 to the intermediate transfer member 70, the secondary transfer roller 5b and the intermediate transfer member cleaning means 6b can be separated from the intermediate transfer member 70. .

  When the superimposed color toner image transferred onto the belt-shaped intermediate transfer member 70 is transferred onto the transfer material P, which is the second image carrier, the secondary transfer roller 5b is brought into contact with the belt of the intermediate transfer member 70. At the same time, the transfer material P is fed from the pair of paper registration rollers 23 through the transfer sheet guide to the belt of the intermediate transfer body 70 to the contact nip with the secondary transfer roller 5b at a predetermined timing. A secondary transfer bias is applied to the secondary transfer roller 5b from a bias power source. By this secondary transfer bias, the superimposed color toner image is transferred (secondary transfer) from the intermediate transfer body 70 to the transfer material P which is the second image carrier. The transfer material P that has received the transfer of the toner image is introduced into the fixing means 24 and heated and fixed.

  The image forming apparatus of the present invention is generally applicable to electrophotographic apparatuses such as electrophotographic copying machines, laser printers, LED printers, and liquid crystal shutter printers, and further displays, recordings, light printing, plate making and facsimiles using electrophotographic technology. The present invention can be widely applied to such devices.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to this. In the following text, “part” means “part by mass”.
(Example 1)
Production of Photoreceptor 1 Photoreceptor 1 was produced as follows.

The surface of the cylindrical aluminum support was cut to prepare a conductive support having a ten-point surface roughness Rz = 1.5 (μm).
<Intermediate layer>
Intermediate layer 1
On the conductive support, the following intermediate layer coating solution was applied by a dip coating method and dried at 120 ° C. for 30 minutes to form an intermediate layer 1 having a dry film thickness of 1.0 μm.

  The following intermediate layer dispersion is diluted twice with the same mixed solvent, and is allowed to stand overnight and then filtered (filter; rigesh mesh filter made by Nippon Pole Co., Ltd., nominal filtration accuracy: 5 microns, pressure: 50 kPa). Produced.

(Preparation of intermediate layer dispersion)
Binder resin: (Exemplary polyamide N-1) 1 part (1.00 volume part)
N-type semiconductive particles: rutile titanium oxide A1 (primary particle size 35 nm; copolymer of methylhydrogensiloxane and dimethylsiloxane (molar ratio 1: 1), in an amount of 5% by mass of the total mass of titanium oxide. Surface treatment) 3.5 parts (1.0 part by volume)
Ethanol / n-propyl alcohol / THF (= 45/20/30 mass ratio) 10 parts The above components were mixed and dispersed in a batch system for 10 hours using a sand mill disperser to prepare an intermediate layer dispersion. .

<Charge generation layer: CGL>
Charge generation material (CGM): CGM-1 of the above-mentioned multistage sublimation purification (mass reduction rate 0.5%)
24 parts polyvinyl butyral resin “S-LEC BL-1” (manufactured by Sekisui Chemical Co., Ltd.) 12 parts 2-butanone / cyclohexanone = 4/1 (v / v) 300 parts The above composition is mixed, dispersed using a sand mill, and charged. A generation layer coating solution was prepared. This coating solution was applied by a dip coating method to form a charge generation layer having a dry film thickness of 0.5 μm on the intermediate layer.

<Charge transport layer (CTL)>
Charge transport material (CTM): 225 parts of the following CTM-1 Polycarbonate (Z300: manufactured by Mitsubishi Gas Chemical Company) 300 parts Antioxidant (AO below) 6 parts THF / toluene mixed solution (volume ratio 3/1 mixture) 2000 parts Silicon 1 part of oil (KF-54: manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed and dissolved to prepare a charge transport layer coating solution 1. This coating solution was applied onto the charge generation layer by a dip coating method and dried at 110 ° C. for 70 minutes to form a charge transport layer 1 having a dry film thickness of 20.0 μm.

Preparation of photoconductors 2 to 5 Except that CGM-1 was changed to the CGM shown in Table 1, the same multi-stage sublimation purification (Purification Example 1) was performed, and then CGM-1 of photoconductor 1 was converted to each CGM. Photoconductors 2 to 5 were produced in the same manner except that the photoconductors 2 to 5 were changed.

Production of Photoreceptor 6 Photoreceptor 6 was produced in the same manner as in production of Photoreceptor 1 except that CGM-1 was changed to the first stage sublimation CGM-1 in Purification Example 1.

Production of Photoreceptor 7 Photoreceptor 7 was produced in the same manner as in production of Photoreceptor 1 except that CGM-1 was synthesized (Synthesis Example 1) and used as it was without purification.

<< Evaluation 1 >>
The electrophotographic photosensitive member thus produced was evaluated as follows using an electrostatic copying paper test apparatus (manufactured by Kawaguchi Electric Co .: EPA-8100).

(sensitivity)
Charge the surface potential of the photoconductor with a corona charger so as to be −700 V, then expose with 400 nm monochromatic light separated by a monochromator, measure the amount of light necessary for the surface potential to decay to −350 V, Sensitivity (E1 / 2) was determined.

  Similarly, the sensitivity in 450 nm and 500 nm monochromatic light was measured.

(Repeat characteristics)
Next, the initial dark portion potential (Vd) and the initial bright portion potential (Vl) are set to around −700 V and −200 V, respectively, and charging and exposure are repeated 3000 times using a monochromatic light of 450 nm, and the fluctuation amount of Vd and Vl ( ΔVd, ΔVl) were measured.

  The results are shown in Table 1.

  In the following table, a minus sign represents a decrease in potential, and a plus sign represents an increase in potential.

(Image evaluation)
As an evaluation machine, a digital copying machine Konica 7085 modified by Konica basically having the configuration shown in FIG. 1 (using a 450 nm semiconductor laser as an image exposure light source, performing a 1200 dpi exposure with a beam diameter of 30 μm, and a process speed of 500 mm / The photoconductors 1 to 9 were mounted on the copying machine and evaluated. Evaluation items and evaluation criteria are shown below.

Evaluation of 1-dot line A 1-dot line and a solid black image were produced on a white A4 paper, and evaluated according to the following criteria.

◎: 1 dot line is reproduced continuously, solid image density is 1.2 or more (good)
○: 1 dot line is reproduced continuously, but solid image density is less than 1.2 to 1.0 or more (no problem in practical use)
×: Even if one dot line is cut and reproduced, or one dot line is reproduced continuously, the image density of solid black is less than 1.0 (there is a problem in practical use)
Evaluation of 2-dot line A 2-dot white line was produced in a solid black image and evaluated according to the following criteria.

A: A white line of 2 dot lines is reproduced continuously, and the solid image density is 1.2 or more (good).
○: The white line of 2 dot lines is reproduced continuously, but the solid image density is less than 1.2 to 1.0 or more (no problem in practical use)
X: Even if the white line of 2 dot lines is cut and reproduced, or the white line of 2 dot lines is reproduced continuously, the solid image density is less than 1.0 (there is a problem in practical use)
The above-mentioned solid image density is measured using RD-918 manufactured by Macbeth. The relative reflection density was measured with the paper reflection density set to “0”. The results are shown in Table 1.

  As is apparent from Table 1, the organic photoreceptors 1 to 5 using the pyrene-based compound of the general formula (1) and the charge generation material of multistage sublimation purification are suitable for irradiation light of 400 to 500 nm such as short wavelength laser light. On the other hand, it has excellent sensitivity characteristics and repeatability, and is excellent in reproducibility of 1-dot lines and 2-dot lines even in image evaluation using a 450 nm short wavelength laser beam. On the other hand, the photoconductor 6 used as the charge generation material of the first-stage sublimation purification and the photoconductor 7 using the charge generation material without purification of the comparative example are also used in the evaluation of sensitivity and repetitive characteristics. 5 is relatively inferior to 5, and in image evaluation, the photoreceptor 6 has a large deterioration in reproducibility of one dot line, and the photoreceptor 7 has a large deterioration in reproducibility of one dot line and two dot lines.

Production of photoconductors 11 to 16 Similar to photoconductor 1 except that multistage sublimation purification of CGM of photoconductor 1 was changed to fractional sublimation purification shown in Table 2 and the mass reduction rate was changed to the exemplified compounds shown in Table 2. Photoconductors 11 to 16 were produced. However, the purification condition of CGM-1 used for the photoreceptor 12 was changed from 1 m to 0.5 m in the length of the temperature gradient in Purification Example 2 (the temperature gradient is the same at about 480 ° C. to about 20 ° C.).

<< Evaluation 2 >>
The evaluations performed on the photoconductors 11 to 16 in the same manner as the photoconductor 1 were performed. The results are shown in Table 2.

  As is clear from Table 2, the organophotoreceptors 11 to 16 using the pyrene compound of the general formula (1) and the charge generation material for fractional sublimation purification are suitable for irradiation light of 400 to 500 nm such as short wavelength laser light. On the other hand, it has excellent sensitivity characteristics and repeatability, and is excellent in reproducibility of 1-dot lines and 2-dot lines even in image evaluation using a 450 nm short wavelength laser beam.

Preparation of photoconductors 21 to 28 CGM multistage sublimation purification of photoconductor 1 was changed to heat treatment in the high boiling point solvents shown in Table 3 (solvents and heating conditions are shown in Table 3), and the mass reduction rate is shown. Photoconductors 21 to 28 were produced in the same manner as Photoconductor 1, except that the exemplified compounds described in 3 were used.

<< Evaluation 3 >>
The evaluations performed on the photosensitive members 21 to 28 in the same manner as in the photosensitive member 1 were performed. The results are shown in Table 3.

  As is clear from Table 3, organic photoconductors 21 to 27 using a charge generating material which is a pyrene compound of the general formula (1) and subjected to a heat treatment in a high boiling point solvent have a 400 wavelength such as a short wavelength laser beam. It has excellent sensitivity characteristics and repeatability with respect to ˜500 nm irradiation light, and is excellent in reproducibility of 1-dot lines and 2-dot lines in image evaluation using 450 nm short-wavelength laser light. On the other hand, the photoconductor 28 used as the charge generation material of the heat treatment in toluene of the comparative example is the photoconductor of the present invention both in evaluation of sensitivity and repetitive characteristics and in reproducibility of 1 dot line and 2 dot line. Relatively inferior to 21-27.

Preparation of photoconductors 31 to 35 Multistage sublimation purification of CGM-1 of photoconductor 1 was changed to the acid paste treatment shown in Table 4 (the purification conditions are all the same as in Purification Example 4), and the mass reduction rate is shown in Table 4 Photoconductors 31 to 35 were produced in the same manner as the photoconductor 1 except that the compound was changed to the exemplified compound.

<< Evaluation 4 >>
The evaluation was performed on the photoconductors 31 to 35 in the same manner as the photoconductor 1 in Evaluation 1. The results are shown in Table 4.

  As is clear from Table 4, the organophotoreceptors 31 to 35 using the pyrene-based compound of the general formula (1) and the charge generation material of the acid paste treatment are suitable for irradiation light of 400 to 500 nm such as short wavelength laser light. On the other hand, it has excellent sensitivity characteristics and repeatability, and is excellent in reproducibility of 1-dot lines and 2-dot lines even in image evaluation using a 450 nm short wavelength laser beam.

1 is a schematic view in which functions of an image forming apparatus of the present invention are incorporated. 1 is a cross-sectional configuration diagram of a color image forming apparatus showing an embodiment of the present invention. 1 is a cross-sectional view of a color image forming apparatus using an organic photoreceptor of the present invention.

Explanation of symbols

10Y, 10M, 10C, 10Bk Image forming unit 1Y, 1M, 1C, 1Bk Photoconductor 2Y, 2M, 2C, 2Bk Charging unit 3Y, 3M, 3C, 3Bk Exposure unit 4Y, 4M, 4C, 4Bk Developing unit

Claims (8)

In thermal mass spectrometry, the mass decrease rate D400 at 400 ° C. defined by the following formula is 1.0% or less, and contains at least one of the compounds of the following general formulas (1) to (3). Pyrene compounds.
D400 = {(Gi−G400) / Gi} × 100
However, Gi is the mass at the start of measurement, and G400 is the mass at 400 ° C.

(In the general formulas (1) to (3), X represents a substituted or unsubstituted divalent aromatic group or heterocyclic group, and R represents a substituted or unsubstituted monovalent aromatic group or heterocyclic group. To express.) The pyrene compound according to claim 1, which is obtained by multi-stage sublimation purification. The pyrene compound according to claim 1, which is obtained by fractional sublimation purification. The pyrene compound according to claim 1, which is obtained by heat treatment in a high boiling point organic solvent. The pyrene compound according to claim 1, which is obtained by acid paste treatment. In an organic photoreceptor having a photosensitive layer on a conductive support, the photosensitive layer has a mass reduction rate D400 at 400 ° C. defined by the following formula of 1.0% or less, and the general formulas (1) to (3): And at least one pyrene compound.
D400 = {(Gi−G400) / Gi} × 100
However, Gi is the mass at the start of measurement, and G400 is the mass at 400 ° C.

(In the general formulas (1) to (3), X represents a substituted or unsubstituted divalent aromatic group or heterocyclic group, and R represents a substituted or unsubstituted monovalent aromatic group or heterocyclic group. To express.) Development that has an exposure step of forming an electrostatic latent image on an organic photoreceptor using a semiconductor laser having an oscillation wavelength of 350 to 500 nm or a light source of a light emitting diode, and developing the electrostatic latent image into a toner image In the image forming method having a step, the organic photoreceptor has a photosensitive layer on a conductive support, and the mass reduction rate D400 at 400 ° C. defined by the following formula is 1.0% or less. And an image forming method comprising: at least one pyrene compound represented by the following general formulas (1) to (3):
D400 = {(Gi−G400) / Gi} × 100
However, Gi is the mass at the start of measurement, and G400 is the mass at 400 ° C.

(In the general formulas (1) to (3), X represents a substituted or unsubstituted divalent aromatic group or heterocyclic group, and R represents a substituted or unsubstituted monovalent aromatic group or heterocyclic group. To express.) Development having an exposure means for forming an electrostatic latent image on an organic photoreceptor using a semiconductor laser having an oscillation wavelength of 350 to 500 nm or a writing light source of a light emitting diode, and developing the electrostatic latent image into a toner image In the image forming apparatus having the means, the organic photoreceptor has a photosensitive layer on the conductive support, and the mass reduction rate D400 at 400 ° C. defined by the following formula is 1% or less, An image forming apparatus comprising at least one pyrene compound represented by the following general formulas (1) to (3):
D400 = {(Gi−G400) / Gi} × 100
However, Gi is the mass at the start of measurement, and G400 is the mass at 400 ° C.

(In the general formulas (1) to (3), X represents a substituted or unsubstituted divalent aromatic group or heterocyclic group, and R represents a substituted or unsubstituted monovalent aromatic group or heterocyclic group. To express.)

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